Heterocyclic immonium group containing azo dyes

ABSTRACT

DYES OF THE FORUMLA   (3-R1,4-(R4-N(-R5)-CO-CH(-R3)-CH2-N(-R5)-)PHENYL)-N=N-   C&lt;(-W1-) A(-)   WHEREIN R1 IS HYDROGEN, HALO, ALKYL, SUBSTITUTED ALKYL, ALKOXY OR SUBSTITUTED ALKOXY, R2 IS HYDROGEN, ALKYL, SUBSTITUTED ALKYL, ARYL, SUBSTITUTED ARYL OR   -CH2-CH(-R3)-CO-N(-R4)-R5   R3 IS HYDROGEN, ALKYL OR SUBSTITUTED ALKYL, EACH OF R4 AND R5 IS INDEPENDENTLY HYDROGEN, ALKYL, SUBSTITUTED ALKYL, CYCLOALKYL, SUBSTITUTED CYCLOALKYL, ARYL OR SUBSTITUTED ARYL. -C&lt;(-W1-) IS A HETEROCYCLIC RING CONTAINING AT LEAST ONE QUATERNARY NITROGEN GROUP, E.G., BENZOTHIAZOLIUM IMIDAZOLIUM, IDAZOLIUM, PYRAZOLIUM, OXAZOLIUM, ISOXAZOLIUM, PYRIDIAZINIUM AND THIAZOLIUM, AND SUBSTITUTED DERIVATIVES THEREOF, AND AO IS AN ANION. THE DYES ARE SUITABLE FOR DYEING AND PRINTING POLYACRYLONITRILE AND ACRYLONITRILE COPOLYMER FIBERS. RESULTING DYEINGS HAVE GOOD FASTNESS TO LIGHT, WASHING, PERSPIRATION, SUBLIMATION, STEAMING, WATER AND CROSS-DYEING.

United States Patent 3,763,140 HETEROCYCLIC IMMONIUM GROUP CONTAININGAZO DYES Roland Entschel, Basel, and Viktor Kaeppeli, AllschwilBasel-Land, Switzerland, assignors to Sandoz Ltd., Basel, Switzerland N0Drawing. Filed Feb. 13, 1970, Ser. No. 11,350 Claims priority,application Switzerland, Mar. 4, 1969, 3,332/69; Apr. 8, 1969, 5,343/69,5,344/69; Jan. 21, 1970, 798/70; Jan. 22, 1970, 839/70; Jan. 23, 1970,

Int. Cl. C09b 29/06, 43/00, 43/06 US. Cl. 260-158 22 Claims ABSTRACT OFTHE DISCLOSURE Dyes of the formula wherein R is hydrogen, halo, alkyl,substituted alkyl, alkoxy or substituted alkoxy,

R is hydrogen, alkyl, substituted alkyl, aryl, substituted aryl or R ishydrogen, alkyl or substituted alkyl,

each of R and R is independently hydrogen, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, aryl or substituted aryl,

This invention relates to basic azo dyes containing cycloimmonium groupswhich are eminently suitable for dyeing and printing polyacrylonitrileand acrylonitrile copolymer fibres and the polyacrylonitrile oracrylonitrile copolymer fibre component of blend yarns and fabrics.

These new dyes are of the formula where R, stands for hydrogen, halogenor an alkyl or alkoxy radical which may be substituted,

3,763,140 Patented Oct. 2, 1973 R for hydrogen or an alkyl or arylradical which may be substituted or a group of the formula R forhydrogen or an alkyl radical which may be substituted,

R and R stands for hydrogen or an alkyl, cycloalkyl or aryl radicalwhich may be substituted,

W for a constituent of a multi-membered ring which contains at least onequaternary nitrogen atom and may contain further hetero atoms andsubstituents and on which further cycloaliphatic, heterocyclic oraromatic rings may be condensed, and

A for an anion.

In this formula the radicals R and R and/or the radicals R and Rtogether with the N atom bound to R or R respectively, may formheterocycles and the aromatic ring B may be further substituted bynon-watersolubilizing substituents.

More specifically, the new dyes have the formula R is alkyl, substitutedalkyl, cyclohexyl or phenyl,

R is hydrogen, halo, alkyl, substituted alkyl, alkoxy or substitutedalkoxy,

R is halo, alkyl, substituted alkyl, alkoxy, substituted alkoxy, cyano,nitro, alkylsulfonyl, substituted alkylsulfonyl, phenylsulfonyl,substituted phenylsulfonyl, naphthylsulfonyl, substitutednaphthylsulfonyl, tetrahydronaphthylsulfonyl or substitutedtetrahydronaphthylsulfonyl,

R is hydrogen, alkyl, substituted alkyl, phenyl, substituted phenyl,naphthyl, substituted naphthyl, tetrahydronaphthyl substitutedtetrahydronaphthyl or R is hydrogen, alkyl or substituted alkyl,

each R and each R independently is hydrogen, alkyl, substituted alkyl,cyclohexyl, substituted cyclohexyl, phenyl, substituted phenyl,naphthyl, substituted naphthyl substituted tetrahydronaphthyl or thyl,

R is alkyl, substituted alkyl, phenyl, substituted phenyl, naphthyl,substituted naphthyl, tetrahydronaphthyl or substitutedtetrahydronaphthyl,

R is phenyl or substituted phenyl,

R is alkyl or substituted alkyl,

K is halo, alkyl, substituted alkyl, alkoxy, cyano, nitro,alkylsulfonyl, substituted alkylsulfonyl, phenylsulfonyl, substitutedphenysulfonyl, naphthylsulfonyl, substituted naphthylsulfonyl,tetrahydronaphthylsulfonyl or substituted tetrahydronaphthylsulfonyl,

L is hydrogen or nitro, with the proviso that only one L can be nitro,

M is hydrogen or methyl,

m is or 1,

n is 0 or 1, and

A is an anion,

wherein each substituent of substituted alkyl, substituted alkoxy,

substituted alkylsulfonyl and substituted cyclohexyl independently ishalo, hydroxy, cyano, phenyl, substituted phenyl, naphthyl, substitutednaphthyl, tetrahydronaphthyl or substituted tetrahydronaphthyl,

each substituent of substituted phenyl, substituted naphthyl,substituted tetrahydronaphthyl, substituted phenoxy, substitutednaphthyloxy, substituted tetrahydronaphthyloxy, substitutedphenylsulfonyl, substituted naphthylsulfonyl and substitutedtetrahydronaphthylsulfonyl independently is halo, hydroxy, cyano, alkyl,alkoxy or phenyl,

each alkyl and alkyl chain of substituted alkyl, alkylsulfonyl andsubstituted alkylsulfonyl independently has 1 to 12 carbon atoms, and

each alkoxy and alkyl chain of substituted alkoxy independently has 1 to6 carbon atoms.

Those compounds wherein R is hydrogen, ahlo, alkyl, substituted alkyl oralkoxy, R is halo, alkyl, substituted alkyl, alkoxy, cyano, nitro,

methylsulfonyl, ethylsulfonyl or phenylsulfonyl, R is hydrogen, alkyl,substituted alkyl, phenyl or each R and each R independently ishydrogen, alkyl, substituted alkyl, cyclohexyl, trimethylcyclohexyl orphenyl, and

each substituent of substituted lalkyl independently is halo, hydroxy,cyano or phenyl are preferred, with those compounds wherein R is alkyl,

R is hydrogen, halo, alkyl or alkoxy,

R is halo, alkyl or alkoxy,

R is hydrogen or alkyl,

each substituted alkyl is monosubstituted alkyl and the substituent ofeach monosubstituted alkyl independently is hydroxy or phenyl,

each alkyl and alkyl chain of substituted alkyl independently has 1 to 4carbon atoms, and

each alkoxy independently has 1 to 3 carbon atoms being particularlypreferred.

The new dyes can be produced by quaternation of a compound of theformula where W represents a constituent of a multi-membered ring whichcontains at least one quaternatable nitrogen atom and may containfurther hetero atoms and substituents and on which furthercycloaliphatic, heterocyclic or aromatic rings may be condensed.

Dyes of good quality conform to the formula iii. R3 R4 where Rrepresents a hydrocarbon radical which may be substituted, and Z aconstituent of a ring which may be further substituted.

Other dyes of comparable quality have the formula Y represents aconstituent of a fiveor six-membered ring which may be substituted and Xa sulphur or nitrogen atom, the latter of which may be substituted.

Similarly good dyes are of the formula lea R represents an alkyl or arylradical which may be substituted and the aromatic ring D may besubstituted by non-watersolubilizing substituents;

of the formula R is hydrogen, halo, alkyl or alkoxy,

R is hydrogen, halo, alkyl or alkoxy,

R is hydrogen, alkyl, monosubstituted alkyl, phenyl wherein R ishydrogen, alkyl (preferably methyl) alkoxy (preferably methoxy) orchloro,

R is hydrogen, alkyl (preferably methyl), alkoxy (preferably meth'oxy)or halo,

R is hydrogen, alkyl, fi-hydroxyethyl, benzyl, pheny RI 0 /B4 GH1-( 3H-N R is hydrogen or methyl, each R independently is hydrogen, alkyl,benzyl, phenyl,

cyclohexyl or 3,3,5-trimethy1cyclohexyl, and R is hydrogen, and of theformula R1 IQ u N b CHz-F H-CO-NH-Rr /C-N-N A ReO R s a v1 where Rstands for methyl or ethyl,

R for hydrogen, halogen or an alkyl or alkoxy radical which may besubstituted,

R for hydrogen or an alkyl or alkoxy radical which may be substituted,

R for an alkyl or aryl radical which may be substituted or for a groupof the formula Rn -GH:(JH-C O-NH-Rt and R for hydrogen or methyl.

Particularly good dyes conform to the formula I N R CHr-CHr-CO-NH:

a Ru and the aromatic rings D and B bear no further substituents;

6 and in particular dyes of the formula /CH:CHa-'CONH| D1| C-N-N N\ 9 Rcm-cm-oo-NH,

(VIII) Dyes of similarly good quality are of the formula a) R: /R4 /NcHl-bH-c 0N A lv-rr c-N=N B N B,

MY Rr where R represents hydrogen or a hydrocarbon radical which may besubstituted, e.g. an optionally substituted alkyl or phenyl radical;

of the formula R11 89 Re J) /N\ /CH: H-CO-NH-Rt e RN ON=N B N A R10 Rnand of the formula R13 69' R14 /N\ /CHzCHg-CONH2 R-I- I o-N=N N\ A whereR" represents methyl or ethyl.

Equally good dyes are of the formula Rs R4 CH H 00 N u G3 CN=N B N Rs A6R1sN\ \:R III R: 2 R" (XII) or of the formula R11 1!: R R: 0 /R4 e/crn-bH-ii-N A E i-N R A CN=N N\ R5 where R represents a phenyl radicalwhich may be substituted R an alkyl radical which may be substituted andR an alkyl radical which may be substituted.

7 Preferably,

each substituted alkyl is monosubstituted alkyl,

each alkyl and alkyl chain of monosubstituted alkyl has 1 to 4 carbonatoms,

each al-koxy independently has 1 to 3 carbon atoms, and

R is hydrogen.

Similarly good dyes are of the formula R BE CH 5; 00 NH R l R v-C z eCN=N B N 9 R18- \R A N R 10 1'1 (XIII) preferably wherein R is phenyl, Ris alkyl, and R19 iS alkyl. and of the formula on on 00 NH R 26 Rzr C Ia 2 C-N=N B; N 6 R21- \R A.

1}} R24 R (XIV) where The new dyes of the formula III can be produced byreacting a compound of formula with a quaternating agent, e.g. acompound of the formula R-A (XVI) where -A representing a radical whichis convertible into an anion A The new dyes of Formulae I and III, andin particular those of Formula DC, can also be produced by the oxidativecoupling of hydrazones of heterocyclic compounds, whose radicals are ofthe formula wlea o] A9 (XVII) vnrx or of functional derivatives of thesehydrazones, with amines of the formula Dyes of Formula XII can besynthesized by reacting a compound of formula with a quaternating agent,e.g. a compound of the R A (XXII) where A represents a radical which isconvertible into an anion A The anion A in the compounds of Formula Ican be replaced by other anions, e.g. with the aid of an ion exchangeror by reaction with salts or acids, if necessary in more than one stage,e.g. via the hydroxide.

The anion A may be an organic or an inorganic ion, e.g. the ion of ahalogen, such as chloride, bromide or iodide; or of sulphate,disulphate, methyl sulphate, aminosulphonate, perchlorate, carbonate,bicarbonate, phosphate, phosphorus tungstate, phosphorus tungsticmolybdate, benzenesulphonate, naphthalenesulphonate,4-chlorobenzenesulphonate, 4-methylbenzenesulphonate, oxalate,maleinate, acetate, propionate, methanesulphonate, lactate, succinate,tartrate, chloracetate, borate or benzoate, or complex ions, such asthat of zinc chloride double'salts.

The quaternation reaction can be effected by the known methods, e.g. inan inert solvent, in a solvent-water mixture or in water alone, atequimolecular ratio or preferably with an excess of the quaternatingagent and with a buffered medium; the range of 20 C. to +200 C. isemployable, but temperatures of 30 C. to C. are preferred for thereaction. The reaction can often be facilitated by the addition of basiccompounds, such as magnesium oxide or sodium acetate.

Examples of suitable quaternating agents are alkyl halides, e.g. methyland ethyl chloride, bromide and iodide; alkylsulphates, e.g. dimethylsulphate; acrylic amides/ hydrogen halides, e.g. CH =CHCO-NH /HCI;epoxides, e.g. ethylene oxide, propylene oxide; epichlorohydrin.

The oxidative coupling reaction can be carried out by any of the knownmethods.

The compounds of FormulaI are preferably free from Water-solubilizingsubstituents. In particular they are free sulfo groups, though they maybear one carboxy group.

In every instance halogen represents chlorine, bromine, fluorine oriodine.

The alkyl radicals generally contain 1 to 12, or 1 to 6 or preferably 1,2, 3 or 4 carbon atoms. If these radicals are substituted they may bear,in particular, halogen atoms,

hydroxyl or cyanogroups or aryl radicals,.for example phenyl radicals.In such cases alkyl represents an aralkyl radical, e.g. a benzylradical.

The aryl radicals, such as phenyl, naphthyl or tetrahydronaphthylradicals, maybe substituted, in particular by halogen atoms, hydroxyl orcyano groups, alkyl or alkoxy radicals, or by aryl radicals, such asphenyl radicals.

The alkoxy radicals may bear 1 to 6 or, preferably, 1, 2 or 3 carbonatoms.

The hydrocarbon radicals may be optionally substituted alkyl, cycloalkylor aryl radicals, e.g. cyclohexyl or phenyl radicals.

Examples of non-water-solubilizing substituents are halogen atoms,optionally substituted alkyl and alkoxy radicals, preferably lowerradicals, the cyano or the nitro group, an optionally substitutedalkylor arylsulphonyl group, e.g. a methyl, ethyl or phenylsulphonylradical, an acylated amino group, a substituted sulphonic acid amidegroup, e.g. a disubstituted sulphonic acid amide group.

Examples of heterocyclic, preferably fiveor six-membered ring systemsbased upon the structures are thiazoles, such as benzothiazoles,thiadiazoles, indazoles, imidazoles, oxazloles, isoxazoles, pyrazoles,pyridines and quinolines.

The amines of Formula XX can be formed by reacting a substituted orunsubstituted l-aminobenzeue with 1 or 2 moles of an acrylamide.Compounds of Formula II or XV can be obtained by coupling the diazocompound of a heterocyclic amine with a coupling component of FormulaXX.

The new dyes are employed for dyeing and printing polyacrylonitrile andacrylonitrile copolymer fibres, the

polyacrylonitrile or acrylonitrile copolymer fibre component of blendyarns and fabrics, and textiles made thereof. They can also be dyed andprinted on polyamide and polyester fibres modified by the introductionof an acid group. Polyamide fibres of this type are known, for example,from Belgian Pat. 706,104 and the corresponding polyester fibres fromUS. Pats. 3,018,272 and 3,379,723. Further, the dyes are suitable fordyeing leather and paper.

The dyes are best applied from aqueous neutral or acid medium in thetemperature range of 60100 C. or at temperatures above 100 C. withpressure. They give level dyeings without the assistance of retarders.

io-O The dyes of this disclosure which have good solubility in organicsolvents are suitable for the coloration of natural and synthetic resinsand of plastics in he dissolved dyeing tannin-treated cotton,regenerated cellulosic fibres and polyamide fibres. It has been foundthat mixturesof two or more of the new dyes and mixtures of these withother cationic dyes can be employed with good success.

The dyeings obtained with the new dyeshave good light fastness, havegood fastness to wet treatments, e.g. washing, perspiration,sublimation, pleating, decatizing, pressing, steaming, water, sea water,cross dyeing and solvents show good compatibility with salts and arewell suited, especially in water. They are stable to boiling and to pHconditions and reserve wool. In comparison with the next comparable dyesof US. Pat. 3,132,132, the dyes of Formula I have better level dyeingproperties and better light fastness on polyacrylonitrile fibres.

In the following examples the parts and percentages are by weight andthe temperatures are given in degrees centigrade.

EXAMPLE 1 9.6 parts of a compound of the formula EXAMPLE 2 44.1 parts ofa compound of the formula CHz-CHz-CO-NH:

are stirred into 300 parts of glacial acetic acid, 4.1 parts ofmagnesium oxide are added and the mixture is raised to 6070. In 45minutes 25.2 parts of dimethyl sulphate are dropped in so that thetemperatures remains constant, then stirring is continued for 3 hours atSubsequently the mixture is stirred into 2000 parts of water and the dyeprecipitated by the addition of 200 parts of common salts and 28 partsof zinc chloride, filtered olf and washed with 5% sodium chloridesolution. On polyacrylonitrile fibres level blue dyeings with goodfastness to'light and wet treatments are obtained with this dye.

Additional dyes are set forth in Table 1. They can be produced by theprocedures of Example 1 or 2 and have the formula where R to R have thesignificance given them in the table.

The anion A may be any one of those named in the and undissolved state.A number can be employed for 75 specification.

In the following Table 2 the structures of additional y are set forthycan be Produced y the p are stirred into 100 parts of glacial aceticacid; 1.1 parts of cedures of Examples 1 or 2 and have the formula whereR to R X Y and Z have the meanings given 40 magnesium oxide are added,thereto; the resulting mixture is raised to and 6.3 parts of dimethylsulphate are added in the course of 30 minutes. Stirring is continuedfor 2-3 hours at -75 following which the mixture is unloaded into 1000parts of water. On the addition of 50 parts of sodium chloride and 7parts of zinc chloride the dye settles out and is filtered off, washedand dried. It gives level violet dyeings on polyacrylonitrile fibreswhich have good fastness to light and wet treatments.

In the following Table 3 the structure of further dyes are indicated.They can be produced by the procedures of TABLE 2 Shade of dyeing onpolyacrylo- 1 Y1 1 40 R41 R42 R4: R44 R45 R46 nitrile fibre Examplenumber:

116 N N CH -CH H --CH; H H C2H5 Blulsh red. 117 N N CH -CH H -CH H H-C:H4CONH Red-violet, 118..- N N CH CH; CH3 -CH CH H C1H4CONH2 D0.119... U. N N CH --CH3 H --CH: H -C(CH3); -C2H4-CONHC (CH D0 120-..- N NN --CH; H -CH; H H --C2H5 Violet. 121"- N N N -CHa H -CH3 H H C2H4-CONH2D0. 122 N N N -CHz H ---CH: -CH: H C2H4CONH2 D0. 123.-- N N N --CH; H-CH Cl H --C2H4CONHz D0. 124.-. N N N --CH3 H CH| OCH: H -C2H4CONH2 D0.125..- N N N CH3 H CH; H -CH1 CzH4CONH-CH; D0. 126 N S OH CH; H H H z 5Bluish red. 127-.. N S CH -CH; H H H --CH: D0. 128.-- N S CH CH; H H H-C2H4CONH: DO. 129 N S CH -CH: H OCH: H C2H|CONH2 Do.

EXAMPLE 130 9.4 parts of a compound of the formula H,o-o--oHCHz-CHg-CONH;

I GHQ-CH3 Examples 1 and 130 and are of the formula where R to R and Rto R have the meanings assigned to them in the table.

68 parts of the intermediate of the formula OZN CH SOi are stirred into500 parts of water. In the course of 45 minutes the solution isconducted at into a mixture of 60 parts of hydrazine-hydrate in 400parts of water. The 1,2-dimethyl 6 nitro-S-indazolonehydrazone settlesout. After stirring for 10 minutes, 120 parts by volume of l/normalhydrochloric acid are added in portions, whereupon the precipitate goesinto solution. The hydrochloride is precipitated by the addition of 100parts of common salt, filtered off with suction and dried. It can bepurified by recrystallization from water.

26 parts of the resultingl,2-dimethyl-6-nitro-3-indazolone-hydrazonehydrochloride are dissolvedin 500 parts of water. A solution of 23.6 parts ofN,N-aniline-bis-propionamide in 40 parts of glacial acetic acid isadded, followed in 30 minutes by a solution of 10 parts of sodiumchloride in 100 parts of water. After stirring for 4 hours at roomtemperature the mixture is raised to 60-70 and the dye precipitated bythe addition of 150 parts of a saturated common salt solution and 28parts of zinc chloride. On cooling, the precipitate is filtered oif,washed with 10% brine and dried. This dye gives level violet dyeings onpolyacrylonitrile fibres which have good light and wet fastnessproperties.

The dyes of Examples 143 to 146 can be produced in analogy with thisexample; they give dyeings of comparably good quality onpolyacrylonitrile fibres.

EXAMPLE 143 cm-orn-ooNH,

I ion. \N/

CH; reddish violet OHN ON=NON A le CHgCHaCH3CH;

CH; violet EXAMPLE 146 CHz-CHrC 0 NHQ L CHzCHg-CONH2 H300 a blush redEXAMPLE 147 9.75 parts of a compound of the formula EXAMPLE 148 68 partsof the intermediate of the formula 0i 0 i ik cmsoi on: f cm are stirredinto 500 parts of water. In 45 minutes the solution is allowed to cfiowat 0 into a mixture of 60 parts of hydrazine-hydrate in 400 parts ofwater. The l,Z-dimethyl-6-nitro-3-indazolone-hydrazone settles out.After stirring for 10 minutes, 120 parts by volume of 1/normalhydrochloric acid are added in portions, causing the precipitate to gointo solution. The hydrochloride is precipitated with parts of commonsalt, filtered off with suction, and dried. It can be purified byrecrystallization from water.

26 parts of the 1,2-dimethyl-6-nitro-3-indazo1onehydazone-hydrochloridethus formed are dissolved in 500 parts of water. A solution of 19.9parts of N-fl-propion- 9.6 parts of the compound of the formula arestirred into 100 parts of glacial acetic acid, and 1.1 parts ofmagnesium oxide are added to the mixture. After it has been raised to60", 6.3 parts of dimethyl sulphate are added dropwise in 30 minutes.The mixture is then stirred further for 2-3 hours at 75. Subsequently,it is unloaded into 1000 parts of water and the dye is precipitated with50 parts of sodium chloride and 8 parts of zinc chloride, filtered off,washed and dried. This dye dyes polyacrylonitrile fibres in level violetshades which have good fastness to light and wet treatments.

DYEING EXAMPLE A mixture of 20 parts of the dye of Example 1 and partsof dextrin is ground in a ball mill for 48 hours. One part of theresulting preparation is pasted with 1 part of 40% acetic acid; then 200parts of dimineralizzed water are added, with boiling for a short time.The mix- .ture is added to a bath of 7000 parts of demineralized water,with the final addition of 2 parts of glacial acetic acid. parts of afabric of polyacrylonitrile fibre are entered into the bath at 60. Thefabric can, if desired, be pretreated for 10-15 minutes in a bath of8000 parts of water and 2 parts of glacial acetic acid at 60. Thedyebath is raised to 98-100 in 30 minutes and held at the boil for 1hour 30 minutes. On removal, the fabric is washed off. A level bluedyeing with good light and wet fastness properties is obtained.

Formulae of representative dyes of the foregoing examples are asfollows:

EXAMPLE 1 EXAMPLE 2 EXAMPLE 6 EXAMPLE 12 EXAMPLE 18 EXAMPLE 21 Havingthus disclosed the invention what we claim is: 1. A compound of theformula R is alkyl, substituted alkyl, cyclohexyl or phenyl,

R is hydrogen, halo, alkyl, substituted alkyl, alkoxy or substitutedalkoxy,

R is halo, alkyl, substituted alkyl, alkoxy, substituted alkoxy, cyano,nitro, alkylsulfonyl, substituted alkylsulfonyl, phenylsulfonyl,substituted phenylsulfonyl, naphthylsulfonyl, substitutednaphthylsulfonyl, tetrahydronaphthylsulfonyl or substitutedtetrahydronaph thylsulfonyl,

R is hydrogen, alkyl, substituted alkyl, phenyl, substituted phenyl,naphthyl, substituted naphthyl, tetrahydronaphthyl, substitutedtetrahydronaphthyl or R is hydrogen, alkyl or substituted alkyl,

each R and each R independently is hydrogen, alkyl, substituted alkyl,cyclohexyl, substituted cyclohexyl, phenyl, substituted phenyl,naphthyl, substituted naphthyl, tetrahydronaphthyl or substitutedtetrahydronaphthyl,

wherein m is 0 or 1, n is 0 or 1, and A is an anion,

wherein each substituent of substituted alkyl, substituted alkoxy,

substituted alkylsulfonyl and substituted cyclohexyl independently ishalo, hydroxy, cyano, phenyl, substituted phenyl, naphthyl, substitutednaphthyl, tetrahydronaphthyl or substituted tetrahydronaphthyl,

each substituent of substituted phenyl, substituted naphthyl,substituted tetrahydron aphthyl, substituted phenoxy, substitutednaphthyloxy, substituted tetrahydronaphthyloxy, substitutedphenylsulfonyl, substituted naphthylsulfonyl and substitutedtetrahydronaphthylsulfonyl independently is halo, hydroxy, cyano, alkyl,alkoxy or phenyl,

each alkyl and alkyl chain of substituted alkyl alkylsulfonyl andsubstituted alkylsulfonyl independently has 1 to 12 carbon atoms, and

each alkoxy and alkyl chain of substituted alkoxy independently has 1 to6 carbon atoms. 2. A compound according to claim 1 wherein R ishydrogen, halo, alkyl, substituted alkyl or alkoxy,

R is halo, alkyl, substituted alkyl, alkoxy, cyano, nitro,

methylsulfonyl, ethylsulfonyl or phenylsulfonyl,

R is hydrogen, alkyl, substituted alkyl, phenyl or each R and each Rindependently is hydrogen, alkyl, substituted alkyl, cyclohexyl,trimethylcyclohexyl or phenyl, and each substituent of substituted alkylindependently is halo, hydroxy, cyano or phenyl. 3. A compound accordingto claim 2 wherein wherein H 11 l o 1, H ID69 i n I C or 11-1; E

5. A compound according to claim 4 having the formula wherein R ishydrogen or R 21 6. A compound according to claim wherein R is methyl orethyl,

R is hydrogen, halo, alkyl or alkoxy,

R is hydrogen, halo, alkyl or alkoxy,

R is hydrogen, alkyl, monosubstituted alkyl, phenyl wherein R ishydrogen, alkyl, alkoxy or chloro,

R is hydrogen, alkyl, alkoxy or halo,

R is hydrogen, alkyl, fl-hydroxyethyl, benzyl, phenyl R is hydrogen ormethyl,

each R independently is hydrogen, alkyl, benzyl, phenyl,

cyclohexyl or 3,3,S-trirnethylcyclohexyl, and

R is hydrogen.

8. A compound according to claim 7 wherein R is hydrogen, methyl,methoxy or chloro, and R is hydrogen, methyl, methoxy or halo.

9. A compound according to claim 8 wherein R is hydrogen, R is hydrogenor methyl, R is methyl, ethyl, butyl or R is hydrogen, R is hydrogen,and R is methyl or ethyl.

10. A compound according to claim 9 wherein R is 11. A compoundaccording to claim 4 having the formula wherein R is alkyl orsubstituted alkyl.

22 12. A compound according to claim 11 wherein each substituted alkylis monosubstituted alkyl,

each alkyl and alkyl chain of monosubstituted alkyl has 1 to 4 carbonatoms, and

each alkoxy independently has 1 to 3 carbon atoms.

13. A compound according to claim 12 wherein R is hydrogen.

14. A compound according to claim 11 wherein R is hydrogen, alkyl oralkoxy, R is hydrogen, halo, alkyl or alkoxy, R is hydrogen or methyl, Ris hydrogen, R is phenyl, R is alkyl, and R is alkyl.

15. A compound according to claim 14 wherein each alkyl independentlyhas 1 to 4 carbon atoms, and each alkoxy independently has 1 to 3 carbonatoms.

16. A compound according to claim 15 wherein R is hydrogen, R ishydrogen, chloro, methyl or methoxy, R is methyl, ethyl, butyl,

R is hydrogen, R is hydrogen, methyl or ethyl, R is methyl or ethyl, andR is methyl or ethyl.

17. A compound according to claim 9 of the formula 2 5 CHzSO 18. Acompound according to claim 10 of the formula CHz-CHa-CO-NHI l on. cmso.

19. A compound according to claim 9 of the formula HsCO- 20. A compoundaccording to claim 8 of the formula 10 22. A compound according to claim10 of the formula 21. A compound according to claim 9 of the formulaReferences Cited UNITED STATES PATENTS Dickey 260-158 X Suzuki et al.260--158 Hahn et al. 260-158 Wallace et al. 260158 Towle et al. 260-158X Ramonathan 260-158 Wallace et a1 260187 Mohr et al. 260-157 XLoffelman 260-162 X FLOYD DALE HIGEL, Primary Examiner US. Cl. X.R.

841 A; 117138.8 R; 260146 R, 152, 154, 155, 156, 157, 163, 310 C, 558 A,559 A

